High temperature resistant PPS and preparation method thereof

Abstract

This invention relates to the field of polymer composite materials technology, and discloses a high-temperature resistant PPS and its preparation method. The PPS prepared by this invention comprises the following raw materials in parts by weight: 40-60 parts PPS resin, 8-15 parts PPO resin, 15-25 parts glass fiber, 2-5 parts modified montmorillonite, 0.5-0.8 parts compatibilizer, 1-2 parts lubricant, and 0.2-0.5 parts nucleating agent. The modified montmorillonite introduced into this PPS differs from traditional small-molecule antioxidants. It is synthesized by surface grafting copolymerization based on montmorillonite. The introduction of this modified montmorillonite into the PPS results in good heat and oxygen aging resistance at high temperatures.

Description

Technical Field

[0001] This invention relates to the field of polymer composite materials technology, specifically to a high-temperature resistant PPS and its preparation method. Background Technology

[0002] Polyphenylene sulfide (PPS) is a high-performance semi-crystalline thermoplastic engineering plastic with excellent thermal stability, chemical stability, corrosion resistance, and flame retardancy. After glass fiber modification, its heat distortion temperature can reach over 260℃, its long-term service temperature can reach 150~170℃, and its maximum service temperature can reach 190℃. Therefore, it has wide applications in electronics, automotive, aerospace, chemical filtration, and machinery manufacturing. However, the sulfur atoms in the PPS molecular chain exist in a -2 valence, and the CSC bond energy is low. In high-temperature environments, it is susceptible to oxygen attack, which can cause breakage and trigger oxidative cross-linking reactions. This leads to unstable viscosity during melt processing, yellowing of the finished product, and decreased impact strength, resulting in performance degradation. During long-term use, tensile strength and impact strength significantly decrease, severely shortening the material's service life.

[0003] Currently, there are two main technical approaches to improving the thermal oxidation stability of PPS: one is to add conventional small-molecule antioxidants (such as hindered phenolic or phosphite antioxidants) to the PPS matrix to inhibit oxidation reactions by capturing free radicals or decomposing hydrogen peroxide during processing and use; the other is to introduce nano-inorganic fillers (such as montmorillonite, silica, etc.) into the PPS matrix to delay oxygen penetration through their physical barrier effect. However, conventional small-molecule antioxidants have low decomposition temperatures and are prone to decomposition or volatilization at processing temperatures of PPS exceeding 300°C, making it difficult to exert the expected antioxidant effect. While traditional inorganic nanofillers can delay oxidation to some extent, their polar surfaces have poor compatibility with the weakly polar PPS matrix, making them prone to aggregation and difficult to achieve uniform nanoscale dispersion. They also lack the chemical antioxidant function of actively scavenging free radicals. Therefore, developing a high-temperature resistant composite antioxidant that can exist stably under high-temperature processing conditions of PPS and can exert a highly efficient antioxidant effect through multiple mechanisms has become an urgent technical problem to be solved in this field. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides a high-temperature resistant PPS and its preparation method.

[0005] The objective of this invention can be achieved through the following technical solutions:

[0006] A high-temperature resistant PPS comprises the following raw materials in parts by weight: 40-60 parts PPS resin, 8-15 parts PPO resin, 15-25 parts glass fiber, 2-5 parts modified montmorillonite, 0.5-0.8 parts compatibilizer, 1-2 parts lubricant, and 0.2-0.5 parts nucleating agent.

[0007] The modified montmorillonite is prepared by the following steps:

[0008] Step A1: Disperse the layered montmorillonite in anhydrous ethanol by ultrasonication for 30 min, then add pre-hydrolyzed KH570 solution, heat to 55-65℃ and reflux for 4.5-6.5 h, filter, wash and dry to obtain pretreated montmorillonite;

[0009] Furthermore, in step A1, the ratio of layered montmorillonite, anhydrous ethanol, and pre-hydrolyzed KH570 solution is 1g:100mL:100mL.

[0010] Further, the pre-hydrolyzed KH570 solution described in step A1 is prepared by stirring 0.05-0.1g of KH570 in a mixture of 90mL ethanol and 10mL deionized water at room temperature for 2h, and the pH of the pre-hydrolyzed KH570 solution is 4-4.2.

[0011] Step A2: Disperse the pretreated montmorillonite in deionized water, add isobutanol and stir until homogeneous, adjust the pH to 9.5, add 2 mg / mL emulsifier OP-10 and stir for 12 h, purge with nitrogen, add sodium bicarbonate and potassium persulfate and stir for 15 min, then slowly add a mixture of methyl methacrylate, functional monomer and toluene, then heat to 75℃ and polymerize for 5-7 h, wash, centrifuge and dry to obtain modified montmorillonite;

[0012] Further, in step A2, the ratio of montmorillonite, deionized water, isobutanol, emulsifier, sodium bicarbonate, potassium persulfate, methyl methacrylate, functional monomer, and toluene used in the pretreatment is 0.5g:50mL:3-6mL:3-5mL:0.3g:0.035-0.04g:1.2-1.6g:0.3-0.6g:10mL;

[0013] Furthermore, the functional monomer described in step A2 is prepared by the following steps:

[0014] Step A21: Under nitrogen protection, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, ethanolamine and DMF are mixed and stirred evenly. Then, concentrated sulfuric acid is slowly added and stirred evenly. The mixture is then heated to 120℃ and refluxed for 6.5-7.5 h. Deionized water is added and shaken for 30 min. The mixture is allowed to stand and separate into layers. The organic phase is collected and washed successively with 0.1 mol / L sodium bicarbonate solution and deionized water. The mixture is then dried under vacuum to obtain the terminal hydroxyl hindered phenol.

[0015] Further, in step A21, the ratio of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, ethanolamine, DMF, and concentrated sulfuric acid is 0.01 mol: 0.01-0.012 mol: 100 mL: 0.04-0.045 mL;

[0016] Step A22: Add cyanuric chloride to acetone and mix and stir evenly in an ice-water bath. Then slowly add 3-buten-1-ol solution and maintain the reaction in an ice-water bath for 3-4 hours. Then raise the temperature to 45°C and slowly add terminal hydroxyl hindered phenol solution. Maintain the temperature for 3-5 hours. Then raise the temperature to 90°C and slowly add 1-amino-5-naphthol solution. Reflux and stir for 6-8 hours. After the reaction is completed, filter, wash and dry to obtain triazine derivative.

[0017] Further, the 3-buten-1-ol solution in step A22 is prepared by mixing and stirring 0.1 mol of 3-buten-1-ol, 3-4 g of sodium hydroxide, and 50 mL of acetone; the hydroxyl-terminated hindered phenol solution is prepared by mixing and stirring 0.1 mol of hydroxyl-terminated hindered phenol, 3-4 g of sodium hydroxide, and 50 mL of acetone; the 1-amino-5-naphthol solution is prepared by mixing and stirring 0.1 mol of 1-amino-5-naphthol, 3-4 g of sodium hydroxide, and 50 mL of acetone.

[0018] Further, the ratio of the amounts of cyanuric chloride, acetone, 3-buten-1-ol solution, hindered hydroxyl-terminated phenol solution and 1-amino-5-naphthol solution in step A22 is 0.1 mol: 50 mL: 50 mL: 50 mL: 50 mL;

[0019] Step A23: Mix the triazine derivative, triethylamine and toluene and stir until homogeneous. Then add diphenylphosphine chloride toluene solution dropwise, maintaining the temperature at 15°C during the dropwise addition. After the dropwise addition is complete, slowly raise the temperature to 80°C and keep the reaction at this temperature for 3-4 hours. Cool to room temperature, filter, and distill under reduced pressure to collect the functional monomer.

[0020] Further, in step A23, the ratio of the triazine derivative, triethylamine, toluene, and diphenylphosphine chloride toluene solution is 0.01-0.011 mol: 0.01-0.011 mol: 30 mL: 20 mL;

[0021] Further, the diphenylphosphine chloride toluene solution mentioned in step A23 is prepared by mixing and stirring 0.01 mol of diphenylphosphine chloride in 20 mL of toluene solution.

[0022] A method for preparing high-temperature resistant PPS includes the following steps:

[0023] Weigh the raw materials according to the weight parts, add PPS resin, PPO resin, modified montmorillonite, compatibilizer, lubricant and nucleating agent into a mixer and mix evenly. Then transfer to a twin-screw extruder, add glass fiber, melt extrude, and granulate to obtain high-temperature resistant PPS.

[0024] The beneficial effects of this invention are:

[0025] The PPS prepared by this invention is composed of PPS resin, PPO resin, modified montmorillonite, compatibilizer, lubricant, nucleating agent and glass fiber. This PPS not only has excellent high temperature resistance, but also good resistance to heat and oxygen aging at high temperatures.

[0026] This invention introduces modified montmorillonite into the PPS to replace traditional small-molecule antioxidants, avoiding the failure of traditional small-molecule antioxidants due to high temperatures, which reduces their thermal oxidation resistance. This allows the material to maintain excellent thermal oxidation resistance even at high temperatures. The modified montmorillonite uses layered montmorillonite as a base, with double bonds modified on its surface. This allows it to undergo free radical polymerization with the double bonds in methyl methacrylate and functional monomers, introducing naphthalene rings, triazine rings, phosphite structures, and hindered phenolic structures. The heat-resistant naphthalene rings and triazine rings improve the overall thermal stability of the molecule, making the antioxidant less prone to decomposition and volatilization at processing temperatures exceeding 300°C in PPS. Its rigid planar structure remains stable at high temperatures and even promotes carbonization, aiding in the formation of a physical protective layer. The hindered phenolic structure and phosphite structure, as core components of the antioxidant, work synergistically to construct a highly efficient cyclical reaction: the hindered phenol captures free radicals, and the phosphite decomposes harmful ROOH while protecting the hindered phenol, allowing it to continue functioning effectively. Furthermore, montmorillonite, as the substrate, acts as a physical barrier in PPS, significantly hindering the diffusion and penetration of oxygen within the material and delaying oxidative degradation. Simultaneously, it also inhibits the migration and volatilization of antioxidant molecules from the material's interior to the surface, extending their effective action time. In addition, modified montmorillonite exhibits good compatibility in the material. This is because the grafted polymer chains act as "molecular bridges," with one end firmly anchored to the montmorillonite surface via chemical bonds; the other end contains aromatic rings (such as naphthalene rings and triazine rings) and thioether groups similar to the chemical structure of PPS, generating strong π-π conjugation with the PPS molecular chains, thereby greatly enhancing the interfacial adhesion between the two phases. Detailed Implementation

[0027] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0028] Example 1: Modified montmorillonite was prepared by the following steps:

[0029] Step A1: Disperse 1g of layered montmorillonite in 100mL of anhydrous ethanol by ultrasonication for 30min, then add 100mL of pre-hydrolyzed KH570 solution, heat to 55℃ and reflux for 4.5h, filter, wash and dry to obtain pretreated montmorillonite. The pre-hydrolyzed KH570 solution is prepared by stirring 0.05g of KH570 in a mixture of 90mL of ethanol and 10mL of deionized water at room temperature for 2h, and the pH of the pre-hydrolyzed KH570 solution is 4.

[0030] Step A2: Disperse 0.5g of pretreated montmorillonite in 50mL of deionized water, add 3mL of isobutanol and stir until homogeneous, adjust the pH to 9.5, then add 3mL of 2mg / mL emulsifier OP-10 and stir for 12h. Purge with nitrogen gas, add 0.3g of sodium bicarbonate and 0.035g of potassium persulfate and stir for 15min. Then slowly add a mixture of 1.6g of methyl methacrylate, 0.3g of functional monomer and 10mL of toluene. Then heat to 75℃ and polymerize for 5h. Wash, centrifuge and dry to obtain modified montmorillonite.

[0031] Furthermore, the functional monomer described in step A2 is prepared by the following steps:

[0032] Step A21: Under nitrogen protection, 0.01 mol of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, 0.01 mol of ethanolamine and 100 mL of DMF were mixed and stirred until homogeneous. Then, 0.04 mL of concentrated sulfuric acid was slowly added and stirred until homogeneous. The mixture was then heated to 120 °C and refluxed for 6.5 h. Deionized water was added and shaken for 30 min. The mixture was allowed to stand and separate into layers. The organic phase was collected and washed successively with 0.1 mol / L sodium bicarbonate solution and deionized water. The mixture was then dried under vacuum to obtain the terminal hydroxyl hindered phenol.

[0033] Step A22: Add 0.1 mol of cyanuric chloride to 50 mL of acetone, mix and stir thoroughly in an ice-water bath, then slowly add 50 mL of 3-buten-1-ol solution, maintain the reaction in an ice-water bath for 3 hours, then raise the temperature to 45°C, slowly add 50 mL of terminal hydroxyl-hindered phenol solution, maintain the temperature for 3 hours, then raise the temperature to 90°C, slowly add 50 mL of 1-amino-5-naphthol solution, reflux and stir for 6 hours. After the reaction is complete, filter, wash, and dry to obtain the triazine derivative. The 3-buten-1-ol solution mentioned in step A22 is prepared by mixing and stirring 0.1 mol of 3-buten-1-ol, 3 g of sodium hydroxide, and 50 mL of acetone; the terminal hydroxyl-hindered phenol solution is prepared by mixing and stirring 0.1 mol of terminal hydroxyl-hindered phenol, 3 g of sodium hydroxide, and 50 mL of acetone; the 1-amino-5-naphthol solution is prepared by mixing 0.1 mol of terminal hydroxyl-hindered phenol, 3 g of sodium hydroxide, and 50 mL of acetone; It is prepared by mixing and stirring 1-amino-5-naphthol, 3g sodium hydroxide and 50mL acetone;

[0034] Step A23: Mix 0.01 mol of triazine derivative, 0.01 mol of triethylamine and 30 mL of toluene and stir until homogeneous. Then add 20 mL of diphenylphosphine chloride toluene solution dropwise, maintaining the temperature at 15°C during the dropwise addition. After the dropwise addition is complete, slowly raise the temperature to 80°C and keep the reaction at this temperature for 3 hours. Cool to room temperature, filter, and distill under reduced pressure to collect the functional monomer. The diphenylphosphine chloride toluene solution is prepared by mixing and stirring 0.01 mol of diphenylphosphine chloride in 20 mL of toluene solution.

[0035] Example 2: Modified montmorillonite was prepared by the following steps:

[0036] Step A1: Disperse 1g of layered montmorillonite in 100mL of anhydrous ethanol by ultrasonication for 30min, then add 100mL of pre-hydrolyzed KH570 solution, heat to 60℃ and reflux for 5.5h, filter, wash and dry to obtain pretreated montmorillonite. The pre-hydrolyzed KH570 solution is prepared by stirring 0.075g of KH570 in a mixture of 90mL of ethanol and 10mL of deionized water at room temperature for 2h, and the pH of the pre-hydrolyzed KH570 solution is 4.1.

[0037] Step A2: Disperse 0.5g of pretreated montmorillonite in 50mL of deionized water, add 4.5mL of isobutanol and stir until homogeneous, adjust the pH to 9.5, then add 4mL of 2mg / mL emulsifier OP-10 and stir for 12h. Purge with nitrogen gas, add 0.3g of sodium bicarbonate and 0.037g of potassium persulfate and stir for 15min. Then slowly add a mixture of 1.4g of methyl methacrylate, 0.45g of functional monomer and 10mL of toluene. Then heat to 75℃ and polymerize for 6h. Wash, centrifuge and dry to obtain modified montmorillonite.

[0038] Furthermore, the functional monomer described in step A2 is prepared by the following steps:

[0039] Step A21: Under nitrogen protection, 0.01 mol of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, 0.011 mol of ethanolamine and 100 mL of DMF were mixed and stirred until homogeneous. Then, 0.043 mL of concentrated sulfuric acid was slowly added and stirred until homogeneous. The mixture was then heated to 120 °C and refluxed for 7 h. Deionized water was added and shaken for 30 min. The mixture was allowed to stand and separate into layers. The organic phase was collected and washed successively with 0.1 mol / L sodium bicarbonate solution and deionized water. The mixture was then dried under vacuum to obtain the terminal hydroxyl hindered phenol.

[0040] Step A22: Add 0.1 mol of cyanuric chloride to 50 mL of acetone, mix and stir thoroughly in an ice-water bath, then slowly add 50 mL of 3-buten-1-ol solution, maintain the reaction in an ice-water bath for 3.5 h, then raise the temperature to 45°C, slowly add 50 mL of terminal hydroxyl-hindered phenol solution, maintain the temperature for 4 h, then raise the temperature to 90°C, slowly add 50 mL of 1-amino-5-naphthol solution, reflux and stir for 7 h. After the reaction is complete, filter, wash, and dry to obtain the triazine derivative. The 3-buten-1-ol solution mentioned in step A22 is prepared by mixing and stirring 0.1 mol of 3-buten-1-ol, 3.5 g of sodium hydroxide, and 50 mL of acetone; the terminal hydroxyl-hindered phenol solution is prepared by mixing and stirring 0.1 mol of terminal hydroxyl-hindered phenol, 3.5 g of sodium hydroxide, and 50 mL of acetone; the 1-amino-5-naphthol solution is prepared by mixing 0.1 mol of terminal hydroxyl-hindered phenol, 3.5 g of sodium hydroxide, and 50 mL of acetone; the 1-amino-5-naphthol solution is prepared by mixing 0.1 mol of... It is prepared by mixing and stirring 1-amino-5-naphthol, 3.5g sodium hydroxide and 50mL acetone;

[0041] Step A23: Mix 0.0105 mol of triazine derivative, 0.0105 mol of triethylamine and 30 mL of toluene and stir until homogeneous. Then add 20 mL of diphenylphosphine chloride toluene solution dropwise, maintaining the temperature at 15°C during the dropwise addition. After the dropwise addition is complete, slowly raise the temperature to 80°C and keep the reaction at this temperature for 3.5 h. Cool to room temperature, filter, and distill under reduced pressure to collect the functional monomer. The diphenylphosphine chloride toluene solution is prepared by mixing and stirring 0.01 mol of diphenylphosphine chloride in 20 mL of toluene solution.

[0042] Example 3: Modified montmorillonite was prepared by the following steps:

[0043] Step A1: Disperse 1g of layered montmorillonite in 100mL of anhydrous ethanol by ultrasonication for 30min, then add 100mL of pre-hydrolyzed KH570 solution, heat to 65℃ and reflux for 6.5h, filter, wash and dry to obtain pretreated montmorillonite. The pre-hydrolyzed KH570 solution is prepared by stirring 0.1g of KH570 in a mixture of 90mL of ethanol and 10mL of deionized water at room temperature for 2h, and the pH of the pre-hydrolyzed KH570 solution is 4.2.

[0044] Step A2: Disperse 0.5g of pretreated montmorillonite in 50mL of deionized water, add 6mL of isobutanol and stir until homogeneous, adjust the pH to 9.5, then add 5mL of 2mg / mL emulsifier OP-10 and stir for 12h. Purge with nitrogen, add 0.3g of sodium bicarbonate and 0.04g of potassium persulfate and stir for 15min. Then slowly add a mixture of 1.2g of methyl methacrylate, 0.6g of functional monomer and 10mL of toluene. Then heat to 75℃ and polymerize for 7h. Wash, centrifuge and dry to obtain modified montmorillonite.

[0045] Furthermore, the functional monomer described in step A2 is prepared by the following steps:

[0046] Step A21: Under nitrogen protection, 0.01 mol of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, 0.012 mol of ethanolamine and 100 mL of DMF were mixed and stirred until homogeneous. Then, 0.045 mL of concentrated sulfuric acid was slowly added and stirred until homogeneous. The mixture was then heated to 120 °C and refluxed for 7.5 h. Deionized water was added and shaken for 30 min. The mixture was allowed to stand and separate into layers. The organic phase was collected and washed successively with 0.1 mol / L sodium bicarbonate solution and deionized water. The mixture was then dried under vacuum to obtain the terminal hydroxyl hindered phenol.

[0047] Step A22: Add 0.1 mol of cyanuric chloride to 50 mL of acetone, mix and stir thoroughly in an ice-water bath, then slowly add 50 mL of 3-buten-1-ol solution, maintain the reaction in an ice-water bath for 4 hours, then raise the temperature to 45°C, slowly add 50 mL of terminal hydroxyl-hindered phenol solution, maintain the temperature for 5 hours, then raise the temperature to 90°C, slowly add 50 mL of 1-amino-5-naphthol solution, reflux and stir for 8 hours. After the reaction is complete, filter, wash, and dry to obtain the triazine derivative. The 3-buten-1-ol solution mentioned in step A22 is prepared by mixing and stirring 0.1 mol of 3-buten-1-ol, 4 g of sodium hydroxide, and 50 mL of acetone; the terminal hydroxyl-hindered phenol solution is prepared by mixing and stirring 0.1 mol of terminal hydroxyl-hindered phenol, 4 g of sodium hydroxide, and 50 mL of acetone; the 1-amino-5-naphthol solution is prepared by mixing 0.1 mol of terminal hydroxyl-hindered phenol, 4 g of sodium hydroxide, and 50 mL of acetone; It is prepared by mixing and stirring 1-amino-5-naphthol, 4g sodium hydroxide and 50mL acetone;

[0048] Step A23: Mix 0.011 mol of triazine derivative, 0.011 mol of triethylamine and 30 mL of toluene and stir until homogeneous. Then add 20 mL of diphenylphosphine chloride toluene solution dropwise, maintaining the temperature at 15°C during the dropwise addition. After the dropwise addition is complete, slowly raise the temperature to 80°C and keep the reaction at this temperature for 4 hours. Cool to room temperature, filter, and distill under reduced pressure to collect the functional monomer. The diphenylphosphine chloride toluene solution is prepared by mixing and stirring 0.01 mol of diphenylphosphine chloride in 20 mL of toluene solution.

[0049] Example 4: A method for preparing high-temperature resistant PPS includes the following steps:

[0050] 40 parts PPS resin, 8 parts PPO resin, 15 parts glass fiber, 2 parts modified montmorillonite prepared in Example 1, 0.5 parts compatibilizer (maleic anhydride grafted ethylene-octene copolymer), 1 part lubricant (polyethylene wax), and 0.2 parts nucleating agent (talc).

[0051] Weigh the raw materials according to the weight parts, add PPS resin, PPO resin, modified montmorillonite prepared in Example 1, compatibilizer, lubricant and nucleating agent into a mixer and mix evenly. Then transfer to a twin-screw extruder, add glass fiber, melt extrude at 290-310℃, and granulate to obtain high-temperature resistant PPS.

[0052] Example 5: A method for preparing high-temperature resistant PPS includes the following steps:

[0053] 50 parts PPS resin, 12 parts PPO resin, 20 parts glass fiber, 3.5 parts modified montmorillonite prepared in Example 2, 0.7 parts compatibilizer (maleic anhydride grafted ethylene-octene copolymer), 1.5 parts lubricant (polyethylene wax), and 0.35 parts nucleating agent (calcium carbonate).

[0054] Weigh the raw materials according to the weight parts, add PPS resin, PPO resin, modified montmorillonite prepared in Example 2, compatibilizer, lubricant and nucleating agent into a mixer and mix evenly. Then transfer to a twin-screw extruder, add glass fiber, melt extrude at 290-310℃, and granulate to obtain high-temperature resistant PPS.

[0055] Example 6: A method for preparing high-temperature resistant PPS includes the following steps:

[0056] 60 parts PPS resin, 15 parts PPO resin, 25 parts glass fiber, 5 parts modified montmorillonite prepared in Example 3, 0.8 parts compatibilizer (maleic anhydride grafted ethylene-octene copolymer), 2 parts lubricant (polyethylene wax), and 0.5 parts nucleating agent (talc or calcium carbonate).

[0057] Weigh the raw materials according to the weight parts, add PPS resin, PPO resin, modified montmorillonite prepared in Example 3, compatibilizer, lubricant and nucleating agent into a mixer and mix evenly. Then transfer to a twin-screw extruder, add glass fiber, melt extrude at 290-310℃, and granulate to obtain high temperature resistant PPS.

[0058] Comparative Example 1: This comparative example is a high-temperature resistant PPS. The difference between this example and Example 6 is that layered montmorillonite is used instead of the modified montmorillonite prepared in Example 3. All other aspects are the same.

[0059] Comparative Example 2: This comparative example is a high-temperature resistant PPS. The difference between it and Example 6 is that methyl methacrylate is used instead of functional monomers in the modified montmorillonite of Example 3, while the rest are the same.

[0060] Comparative Example 3: This comparative example is a high-temperature resistant PPS. The difference from Example 6 is that 1.5 parts of commercially available antioxidant 1010 are used instead of the modified montmorillonite prepared in Example 3.

[0061] The high-temperature resistant PPS prepared in Examples 4-6 and Comparative Examples 1-3 were subjected to performance tests:

[0062] High temperature resistance test: Referring to GB / T 7141-2008 "Test Method for Thermal Aging of Plastics", the test strips were placed in an oven at 200℃ for continuous aging, and samples were taken at different times of 168h, 240h and 500h to test the tensile strength retention rate.

[0063] Heat distortion temperature: The heat distortion temperature (1.8 MPa) of all the above samples was tested according to the ISO 75 international testing standard.

[0064] The test results are shown in Table 1:

[0065] Table 1: Performance Test Results

[0066]

[0067] As can be seen from Table 1, the PPS prepared by this invention not only has excellent high temperature resistance, but also excellent heat oxidation resistance.

[0068] The above content is merely an example and illustration of the concept of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the scope defined by the inventive concept, they should all fall within the protection scope of the present invention.

Claims

1. A high-temperature resistant PPS, characterized in that, The raw materials include the following parts by weight: 40-60 parts PPS resin, 8-15 parts PPO resin, 15-25 parts glass fiber, 2-5 parts modified montmorillonite, 0.5-0.8 parts compatibilizer, 1-2 parts lubricant, and 0.2-0.5 parts nucleating agent. The modified montmorillonite is prepared by the following steps: Step A1: Disperse the layered montmorillonite in anhydrous ethanol by ultrasonication for 30 min, then add pre-hydrolyzed KH570 solution, heat to 55-65℃ and reflux for 4.5-6.5 h, filter, wash and dry to obtain pretreated montmorillonite; Step A2: Disperse the pretreated montmorillonite in deionized water, add isobutanol and stir until homogeneous, adjust the pH to 9.5, add 2 mg / mL emulsifier OP-10 and stir for 12 h, purge with nitrogen, add sodium bicarbonate and potassium persulfate and stir for 15 min, then slowly add a mixture of methyl methacrylate, functional monomer and toluene, then heat to 75℃ and polymerize for 5-7 h, wash, centrifuge and dry to obtain modified montmorillonite; The functional monomer is prepared by reacting a triazine derivative with diphenylphosphine chloride. The triazine derivative is prepared by reacting cyanuric chloride with 3-buten-1-ol, a hydroxyl-terminated hindered phenol, and 1-amino-5-naphthol. The hydroxyl-terminated hindered phenol is prepared by reacting 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with ethanolamine.

2. The high-temperature resistant PPS according to claim 1, characterized in that, In step A1, the ratio of layered montmorillonite, anhydrous ethanol, and pre-hydrolyzed KH570 solution is 1g:100mL:100mL. The pre-hydrolyzed KH570 solution is prepared by stirring 0.05-0.1g of KH570 in a mixture of 90mL of ethanol and 10mL of deionized water at room temperature for 2 hours, and the pH of the pre-hydrolyzed KH570 solution is 4-4.

2.

3. The high-temperature resistant PPS according to claim 1, characterized in that, In step A2, the ratio of montmorillonite, deionized water, isobutanol, emulsifier, sodium bicarbonate, potassium persulfate, methyl methacrylate, functional monomer, and toluene used in the pretreatment is 0.5g:50mL:3-6mL:3-5mL:0.3g:0.035-0.04g:1.2-1.6g:0.3-0.6g:10mL.

4. The high-temperature resistant PPS according to claim 1, characterized in that, The functional monomer mentioned in step A2 is specifically prepared by the following steps: Step A21: Under nitrogen protection, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, ethanolamine and DMF are mixed and stirred evenly. Then, concentrated sulfuric acid is slowly added and stirred evenly. The mixture is then heated to 120℃ and refluxed for 6.5-7.5 h. Deionized water is added and shaken for 30 min. The mixture is allowed to stand and separate into layers. The organic phase is collected and washed successively with 0.1 mol / L sodium bicarbonate solution and deionized water. The mixture is then dried under vacuum to obtain the terminal hydroxyl hindered phenol. Step A22: Add cyanuric chloride to acetone and mix and stir evenly in an ice-water bath. Then slowly add 3-buten-1-ol solution and maintain the reaction in an ice-water bath for 3-4 hours. Then raise the temperature to 45°C and slowly add terminal hydroxyl hindered phenol solution. Maintain the temperature for 3-5 hours. Then raise the temperature to 90°C and slowly add 1-amino-5-naphthol solution. Reflux and stir for 6-8 hours. After the reaction is completed, filter, wash and dry to obtain triazine derivative. Step A23: Mix the triazine derivative, triethylamine and toluene and stir until homogeneous. Then add diphenylphosphine chloride toluene solution dropwise, maintaining the temperature at 15°C during the dropwise addition. After the dropwise addition is complete, slowly raise the temperature to 80°C and keep the reaction at that temperature for 3-4 hours. Cool to room temperature, filter, and distill under reduced pressure to collect the functional monomer.

5. The high-temperature resistant PPS according to claim 4, characterized in that, In step A21, the ratio of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, ethanolamine, DMF, and concentrated sulfuric acid is 0.01 mol: 0.01-0.012 mol: 100 mL: 0.04-0.045 mL.

6. The high-temperature resistant PPS according to claim 4, characterized in that, The 3-buten-1-ol solution in step A22 is prepared by mixing and stirring 0.1 mol of 3-buten-1-ol, 3-4 g of sodium hydroxide, and 50 mL of acetone; the hydroxyl-terminated hindered phenol solution is prepared by mixing and stirring 0.1 mol of hydroxyl-terminated hindered phenol, 3-4 g of sodium hydroxide, and 50 mL of acetone; and the 1-amino-5-naphthol solution is prepared by mixing and stirring 0.1 mol of 1-amino-5-naphthol, 3-4 g of sodium hydroxide, and 50 mL of acetone.

7. The high-temperature resistant PPS according to claim 4, characterized in that, The ratio of cyanuric chloride, acetone, 3-buten-1-ol solution, hindered hydroxyl-terminated phenol solution, and 1-amino-5-naphthol solution in step A22 is 0.1 mol: 50 mL: 50 mL: 50 mL: 50 mL.

8. The high-temperature resistant PPS according to claim 4, characterized in that, In step A23, the ratio of the amount of triazine derivative, triethylamine, toluene, and diphenylphosphine chloride toluene solution is 0.01-0.011 mol: 0.01-0.011 mol: 30 mL: 20 mL.

9. The high-temperature resistant PPS according to claim 4, characterized in that, The diphenylphosphine chloride toluene solution described in step A23 is prepared by mixing and stirring 0.01 mol of diphenylphosphine chloride in 20 mL of toluene solution.

10. A method for preparing high-temperature resistant PPS according to any one of claims 1-9, characterized in that, Includes the following steps: Weigh the raw materials according to the weight parts, add PPS resin, PPO resin, modified montmorillonite, compatibilizer, lubricant and nucleating agent into a mixer and mix evenly. Then transfer to a twin-screw extruder, add glass fiber, melt extrude, and granulate to obtain high-temperature resistant PPS.

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